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WO2019221233A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

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Publication number
WO2019221233A1
WO2019221233A1 PCT/JP2019/019510 JP2019019510W WO2019221233A1 WO 2019221233 A1 WO2019221233 A1 WO 2019221233A1 JP 2019019510 W JP2019019510 W JP 2019019510W WO 2019221233 A1 WO2019221233 A1 WO 2019221233A1
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WIPO (PCT)
Prior art keywords
electrolyte
experimental example
secondary battery
lithium secondary
lithium
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English (en)
Japanese (ja)
Inventor
周平 阪本
陽子 小野
政彦 林
武志 小松
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NTT Inc
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Nippon Telegraph and Telephone Corp
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Priority to US17/055,890 priority Critical patent/US11961960B2/en
Publication of WO2019221233A1 publication Critical patent/WO2019221233A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium secondary battery.
  • Lithium secondary batteries have higher energy density and superior charge / discharge cycle characteristics compared to other secondary batteries such as nickel cadmium secondary batteries and nickel hydride secondary batteries. Widely used as a power source for electronic devices. There are still high demands for downsizing and thinning.
  • Non-Patent Document 1 uses about 1 mmol / 1 LiPF 6 EC / DMC / EMC based on an organic solvent as an electrolyte, LiFePO 4 as a positive electrode, and Li as a counter electrode, so that the current density is about 15 mA / g. It discloses disclosing a capacity of 135 mAh / g.
  • Non-Patent Document 2 discloses that a gel polymer electrolyte based on a hydroxyethyl cellulose membrane is used as an electrolyte, LiFePO 4 is used as a positive electrode, and Li is used as a counter electrode, so that a capacity of about 110 mAh / g is obtained under a current density of 50 mA / g. Disclosed.
  • Non-Patent Document 3 uses a solid electrolyte that is NASICON-type LiZr 2 (PO 4 ) 3 as an electrolyte, LiFePO 4 as a positive electrode, and Li as a counter electrode, so that about 80 ° C. under a current density of 100 ⁇ A / cm 2. It discloses disclosing a capacity of 120 mAh / g.
  • Non-Patent Document 1-3 since the lithium secondary battery disclosed in Non-Patent Document 1-3 has a large resistance at the electrode (positive electrode) -electrolyte interface, it has a smaller capacity than the theoretical capacity of 169 mAh / g of the positive electrode active material. There are challenges.
  • the present invention has been made in view of this problem, and an object thereof is to provide a lithium secondary battery having a high capacity and a long life.
  • a lithium secondary battery includes a positive electrode including a material capable of inserting and extracting lithium ions, a lithium ion conductive electrolyte including a salen metal complex, and lithium metal or lithium ion.
  • a gist is to provide a negative electrode containing a material capable of occlusion and release.
  • the present invention it is possible to provide a lithium secondary battery having a high capacity and a long life by adding a salen metal complex to the electrolyte.
  • FIG. 1 is a schematic cross-sectional view schematically showing a basic configuration of a lithium secondary battery according to an embodiment of the present invention. It is a figure which shows structural formula of a salen type metal complex. It is sectional drawing which shows typically the structure of the lithium secondary battery which concerns on embodiment of this invention. It is a figure which shows the charging / discharging characteristic of the lithium secondary battery of Experimental example 1 and a comparative example.
  • FIG. 1 is a schematic cross-sectional view showing a basic configuration of a lithium secondary battery according to this embodiment.
  • the basic configuration of the lithium secondary battery 100 includes a positive electrode 10, an electrolyte 20, and a negative electrode 30, and is the same as a general lithium secondary battery.
  • the lithium secondary battery according to this embodiment is characterized in that the electrolyte 20 contains a salen metal complex as an additive.
  • the positive electrode 10 can include a catalyst and a conductive material as constituent elements.
  • the positive electrode 10 preferably contains a binder for integrating the catalyst and the conductive material.
  • the negative electrode 30 can have a constituent element such as lithium-containing alloy, carbon, and oxide capable of releasing and absorbing metallic lithium or lithium ions.
  • Electrolyte The electrolyte 20 of the lithium secondary battery 100 according to the present embodiment exhibits lithium ion conductivity, and includes a salen metal complex as an additive.
  • FIG. 2 shows a structural formula of a salen metal complex.
  • the salen metal complex includes (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminotitanium chloride (TiSl), ( R, R)-(-)-N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminovanadium chloride (VSl), (R, R)-(- ) -N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminochromium chloride (CrSl), (R, R)-(-)-N, N'- Bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminomanganese chloride (MnSl), (R, R)-( ⁇ )-
  • one type may be selected from the above, or two or more types may be mixed and used.
  • the mixing ratio in the case of mixing is not specifically limited. Any mixing ratio may be used.
  • the electrolyte 20 contains a Li salt together with the salen metal complex.
  • Li salt is supplied from a metal salt containing lithium.
  • the metal salt include, for example, lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonylamide (LiTFSA) [(CF 3 SO 2 ) 2 NLi], etc. Mention may be made of solute metal salts.
  • the electrolyte 20 contains a solvent.
  • the solvent include dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate (MBC), diethyl carbonate (DEC), and ethyl propyl carbonate (EPC).
  • the mixing ratio in the case of using a mixed solvent is not particularly limited.
  • the electrolyte 20 may include a gel polymer.
  • a gel polymer for example, one of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), and polyethylene oxide (PEO) gel polymer, or a gel polymer in which two or more kinds are mixed may be used.
  • the mixing ratio of the gel polymer is not particularly limited.
  • the electrolyte 20 may include a solid electrolyte.
  • the solid electrolyte is, for example, beta-eucryptite structure LiAlSiO 4, ramsdellite structure of Li 2 Ti 3 O 7, triple rutile structure of LiNb 0.75 Ta 0.25 WO 6, Li 14 ZnGe 4 O 16, Li 3 .6 Ge 0.6 V 0.4 O 4 ⁇ -Li 3 PO 4 structure, Li 5.5 Fe 0.5 Zn 0.5 O 4 inverted fluorite structure, Li 1.3 Ti 1.7 NASICON type of Al 0.3 (PO 4 ) 3 , ⁇ 3 -Fe 2 (SO 4 ) 3 structure of Li 3 Sc 0.9 Zr 0.1 (PO 4 ) 3 , La 2 / 3-x Li 3x TiO 3
  • An oxide solid electrolyte having a perovskite structure of (x ⁇ 0.1) or a garnet structure of Li 7 a 3 Zr 2 O 12 , Li4GeS4, Li4-xGe1-xPx
  • the positive electrode 10 of the lithium secondary battery 100 includes a conductive material capable of inserting and desorbing lithium ions, and includes both or one or both of a catalyst and a binder as necessary. Including.
  • the conductive material contained in the positive electrode 10 is preferably carbon.
  • Examples thereof include carbon blacks such as ketjen black and acetylene black, activated carbon, graphites, carbon fibers, carbon sheets, and carbon cloth.
  • cathode material of the cathode 10 examples include layered rock salt type materials such as LiCoO 2 and LiNiO 2, spinel type materials such as LiMn 2 O 4, and olipine type materials such as LiFePO 4. In addition, it will not specifically limit if it is a well-known positive electrode material other than this.
  • These positive electrode materials can be synthesized using a known process such as a solid phase method or a liquid phase method.
  • the positive electrode 10 may include a binder.
  • the binder is not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and polybutadiene rubber. These binders can be used as a powder or as a dispersion.
  • the conductive material content in the positive electrode 10 is preferably less than 100% by weight based on the weight of the positive electrode 10, for example.
  • the ratio of other components is the same as that of a conventional lithium secondary battery.
  • the positive electrode 10 is produced as follows.
  • the positive electrode 10 may be formed by dispersing the above mixture in a solvent such as an organic solvent to form a slurry, and applying the slurry mixture on a current collector and drying.
  • a hot press may be applied in addition to the cold press for the purpose of increasing the strength of the electrode and preventing leakage of the electrolyte.
  • the positive electrode 10 with more excellent stability can be produced.
  • the positive electrode 10 may be produced by depositing a positive electrode material on the current collector by using a film forming method such as RF (Radio-Frequency) sputtering.
  • RF Radio-Frequency
  • Current collectors include, for example, metals such as metal foil and metal mesh, carbon such as carbon cloth and carbon sheet, ITO (Indium Tin Oxide) with tin oxide added to indium oxide, and ATO doped with antimony in tin oxide An oxide film such as (Sb-doped Tin Oxide) can be given.
  • the negative electrode 30 of the lithium secondary battery 100 includes a negative electrode material.
  • the negative electrode material is not particularly limited as long as it can be used as a negative electrode for a lithium secondary battery.
  • metallic lithium can be mentioned.
  • the negative electrode 30 can be formed by a known method. For example, when lithium metal is used as the negative electrode, a plurality of metal lithium foils may be stacked to form a predetermined negative electrode.
  • the lithium secondary battery 100 includes, in addition to the above-described constituent elements, structural members such as a separator, a battery case, and a metal mesh, and other elements required for the lithium secondary battery. Including.
  • FIG. 3 is a cross-sectional view schematically showing the configuration of the lithium secondary battery 100 according to this embodiment. A method for manufacturing a lithium secondary battery will be described with reference to FIGS.
  • the positive electrode 10 is fixed on the current collector 41 as described in the preparation of the positive electrode (II-4). Further, as described in (III), the negative electrode 30 is fixed on the current collector 42.
  • the electrolyte 20 described in (I) is disposed between the positive electrode 10 and the negative electrode 30. Then, the structure sandwiched between the current collector 41 and the current collector 42 is sealed with a housing 50 such as a laminate so that the lithium secondary battery 100 is not exposed to the atmosphere.
  • a member such as a separator is disposed between the positive electrode 10 and the negative electrode 30.
  • the lithium secondary battery 100 suitable for a use is produced by appropriately arranging other insulating members and fixtures.
  • Battery cycle test In the battery cycle test, a charge / discharge measurement system (manufactured by Bio Logic) is used to pass 1 mA / cm 2 at a current density per area of the positive electrode 10, and the battery voltage rises to 4.0 V from the open circuit voltage. The charging voltage was measured until. The battery discharge test was conducted at the same current density as that during charging until the battery voltage dropped to 2.5V. The charge / discharge test of the battery was performed in a normal living environment. The charge / discharge capacity was expressed as a value per weight (mAh / g) of the positive electrode material.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 1 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane. Diamino titanium chloride (TiSl) is included.
  • TiSl was mixed with the organic electrolyte.
  • dispersion was performed for 10 minutes at maximum output using an ultrasonic cleaner.
  • the organic electrolyte used was a solution of LiPF 6 dissolved in an organic solvent EC: DMC (volume ratio 1: 1) at a concentration of 1 mol / l.
  • the organic electrolyte solution was mixed with 50 mmol / l of TiSl to obtain a TiSl-containing electrolyte.
  • the lithium secondary battery cell was produced in the following procedures.
  • the lithium secondary battery cell was assembled in dry air with a dew point of ⁇ 60 ° C. or lower.
  • the electrolyte of the lithium secondary battery to be compared with the experimental example according to this embodiment uses 1 mol / l LiPF6 / EC: DMC (volume ratio 1: 1) as an organic electrolytic solution contained in the solid electrolyte.
  • the next battery cell was produced in the same manner as in Example 1.
  • FIG. 4 shows the charge / discharge characteristics of the lithium secondary batteries of Experimental Example 1 and Comparative Example.
  • the horizontal axis represents capacity (mAh / g), and the vertical axis represents battery voltage (V).
  • the initial discharge capacity of Experimental Example 1 was 162 mAh / g.
  • the capacity retention rate in the 100th cycle of Experimental Example 1 was 98%.
  • Table 1 shows the initial discharge capacity and the discharge capacity retention rate.
  • the initial discharge capacity of the comparative example was 112 mAh / g. Further, the capacity retention rate at the 100th cycle was 62%.
  • the lithium secondary battery using the TiSl-containing electrolyte improves the battery characteristics.
  • other experimental conditions for evaluating the characteristics will be described.
  • Example 2 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 2 was prepared by mixing TiSl obtained in the same procedure as Experimental Example 1 at a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte.
  • the gel polymer film was prepared by dissolving hydroxyethyl cellulose (manufactured by Aldrich) in water, followed by heating and vacuum drying treatment.
  • the electrolyte 20 was produced by impregnating the obtained gel polymer film with the same organic electrolyte as in Experimental Example 1.
  • Experimental Example 2 the initial discharge capacity was 158 mAh / g, and the discharge capacity retention rate was 96%.
  • the evaluation result of each experimental example is collectively shown in Table 1 described later.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 3 was prepared by mixing TiSl obtained by the same procedure as that of Experimental Example 1 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte.
  • the solid electrolyte Li 2 S (manufactured by Wako Pure Chemical Industries, Ltd.), GeS 2 (manufactured by Wako Pure Chemical Industries, Ltd.) and P 2 S 5 (manufactured by Aldrich) are mixed in a glove box and heated at 700 ° C. for 8 hours. It was prepared by processing.
  • Experimental Example 3 had an initial discharge capacity of 155 mAh / g and a discharge capacity retention rate of 91%.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 4 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane. Contains diaminovanadium chloride (VSl).
  • Experimental Example 4 had an initial discharge capacity of 168 mAh / g and a discharge capacity retention rate of 98%.
  • Example 5 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 5 was prepared by mixing VSl obtained by the same procedure as in Experimental Example 4 at a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte. Experimental Example 5 differs from Experimental Example 2 (TiSl) only in the type of additive (VSl).
  • the initial discharge capacity of Experimental Example 5 was 158 mAh / g, and the discharge capacity retention rate was 94%.
  • Example 6 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 6 was prepared by mixing VSl obtained by the same procedure as in Experimental Example 4 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte. Experimental Example 6 differs from Experimental Example 3 (TiSl) only in the type of additive (VSl).
  • the initial discharge capacity of Experimental Example 6 was 158 mAh / g, and the discharge capacity retention rate was 91%.
  • Example 7 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 7 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane. Diaminochrome chloride (CrSl) is included.
  • Experimental Example 7 differs from Experimental Examples 1 and 4 only in the type of additive (CrSl).
  • Experimental Example 7 had an initial discharge capacity of 168 mAh / g and a discharge capacity retention rate of 97%.
  • Example 8 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 8 was prepared by mixing CrSl obtained in the same procedure as in Experimental Example 7 at a ratio of 30 wt% (electrolyte weight basis) to the gel polymer electrolyte.
  • Experimental Example 8 differs from Experimental Examples 2 and 5 only in the type of additive (CrSl).
  • Experimental Example 8 had an initial discharge capacity of 162 mAh / g and a discharge capacity retention rate of 97%.
  • Example 9 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 9 was prepared by mixing CrSl obtained in the same procedure as Experimental Example 7 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte.
  • Experimental Example 9 differs from Experimental Examples 3 and 6 only in the type of additive (CrSl).
  • Experimental Example 9 had an initial discharge capacity of 158 mAh / g and a discharge capacity retention rate of 96%.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 10 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane.
  • Diaminomanganese chloride (MnSl) is included.
  • Experimental example 10 differs from experimental examples 1, 4 and 7 only in the type of additive (MnSl).
  • the initial discharge capacity was 168 mAh / g, and the discharge capacity retention rate was 94%.
  • Example 11 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 11 was prepared by mixing MnSl obtained in the same procedure as Experimental Example 10 in a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte.
  • Experimental example 11 differs from experimental examples 2, 5, and 8 only in the type of additive (MnSl).
  • the initial discharge capacity was 168 mAh / g, and the discharge capacity retention rate was 92%.
  • Example 12 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 12 was prepared by mixing MnSl obtained in the same procedure as Experimental Example 10 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte.
  • Experimental Example 12 differs from Experimental Examples 3, 6, and 9 only in the type of additive (MnSl).
  • the initial discharge capacity was 165 mAh / g, and the discharge capacity retention rate was 90%.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 13 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane. Contains diaminoiron chloride (FeSl).
  • Experimental Example 13 differs from Experimental Examples 1, 4, 7, and 10 only in the type of additive (FeSl).
  • the initial discharge capacity was 165 mAh / g, and the discharge capacity retention rate was 98%.
  • Example 14 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 14 was prepared by mixing FeSl obtained in the same procedure as Experimental Example 13 at a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte.
  • Experimental Example 14 differs from Experimental Examples 2, 5, 8, and 11 only in the type of additive (FeSl).
  • Experimental Example 14 had an initial discharge capacity of 157 mAh / g and a discharge capacity retention rate of 97%.
  • Example 15 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 15 was prepared by mixing FeSl obtained in the same procedure as Experimental Example 13 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte. Experimental Example 15 differs from Experimental Examples 3, 6, 9, and 12 only in the type of additive (FeSl).
  • Experimental Example 15 had an initial discharge capacity of 156 mAh / g and a discharge capacity retention rate of 94%.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 16 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane. Diaminocobalt (CoSl) is included.
  • CoSl was mixed with the organic electrolyte in the same procedure as in Experimental Example 1.
  • Experimental Example 16 differs from Experimental Examples 1, 4, 7, and 10 only in the type of additive (CoSl).
  • the initial discharge capacity was 159 mAh / g, and the discharge capacity retention rate was 99%.
  • Example 17 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 17 was prepared by mixing CoSl obtained in the same procedure as in Experimental Example 16 at a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte.
  • Experimental Example 17 differs from Experimental Examples 2, 5, 8, and 11 only in the type of additive (CoSl).
  • the initial discharge capacity of Experimental Example 17 was 158 mAh / g, and the discharge capacity retention rate was 91%.
  • Example 18 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 18 was prepared by mixing CoSl obtained by the same procedure as that of Experimental Example 16 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte. Experimental Example 18 differs from Experimental Examples 3, 6, 9, 12, and 15 only in the type of additive (CoSl). The initial discharge capacity of Experimental Example 18 was 156 mAh / g, and the discharge capacity retention rate was 91%.
  • the electrolyte 20 of the lithium secondary battery 100 of Experimental Example 16 is (R, R)-( ⁇ )-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexane.
  • Diaminoruthenium chloride (RuSl) is included.
  • RuSl was mixed with the organic electrolyte in the same procedure as in Experimental Example 1.
  • Experimental Example 19 differs from Experimental Examples 1, 4, 7, 10, 13, and 16 only in the type of additive (RuSl).
  • the initial discharge capacity was 164 mAh / g, and the discharge capacity retention rate was 99%.
  • Example 20 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 20 was prepared by mixing RuSl obtained in the same procedure as in Experimental Example 19 at a ratio of 30 wt% (electrolyte important standard) to the gel polymer electrolyte.
  • Experimental Example 20 differs from Experimental Examples 2, 5, 8, 11, 14, and 17 only in the type of additive (RuSl).
  • Experimental Example 20 had an initial discharge capacity of 164 mAh / g and a discharge capacity retention rate of 94%.
  • Example 21 The electrolyte 20 of the lithium secondary battery 100 of Experimental Example 21 was prepared by mixing RuSl obtained in the same procedure as in Experimental Example 19 at a ratio of 30 wt% (electrolyte important standard) to the solid electrolyte. Experimental Example 21 differs from Experimental Examples 3, 6, 9, 12, 15, and 18 only in the type of additive (RuSl). In Experimental Example 21, the initial discharge capacity was 161 mAh / g, and the discharge capacity retention rate was 90%.
  • the organic electrolyte was a salen-based metal complex at a rate of 50 mmol / l or less (1.0 to 50 mmol / l) based on the volume of the organic electrolyte. Is preferably added.
  • the gel polymer electrolyte and the solid electrolyte are preferably added with a salen metal complex at a ratio of 1.0 wt% or less (1.0 to 30 wt%) based on the weight of the electrolyte.
  • the average of the first discharge capacity of the experimental example is 161 mAh / g
  • the average of the discharge capacity maintenance rate at the 100th cycle of the experimental example is 94.6%, about 1.44 times the capacity of the comparative example (112 mAh / g, 62%), and the capacity The retention rate was about 1.53 times better.
  • a lithium secondary battery having a large discharge capacity and good charge / discharge cycle performance can be provided by including a salen metal complex as an additive in an electrolyte.
  • this invention is not limited to said embodiment, A deformation
  • This embodiment can produce a high-capacity, long-life lithium secondary battery, and can be used as a power source for various electronic devices and automobiles.

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Abstract

La présente invention concerne une batterie secondaire au lithium qui a une capacité supérieure et une durée de vie plus longue. Cette batterie secondaire au lithium est pourvue : d'une électrode positive 10 qui contient un matériau qui est capable d'intercaler et de désintercaler des ions lithium ; d'un électrolyte conducteur d'ions lithium 20 qui contient un complexe métal-salène ; et d'une électrode négative 30 qui contient un matériau qui est capable d'absorber et de désorber des ions lithium ou du lithium métal. Par rapport à cette batterie secondaire au lithium, le complexe métal-salène est choisi parmi (R, R)- (-)-N, N'-bis (3, 5-di-tert-butylsalicylidène) -1, 2-cyclohexanediaminotitanium (TiSl), VSl, CrSl, MnSl, FeSl, CoSl et RuSl.
PCT/JP2019/019510 2018-05-18 2019-05-16 Batterie secondaire au lithium Ceased WO2019221233A1 (fr)

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JP2018096015A JP6982244B2 (ja) 2018-05-18 2018-05-18 リチウム二次電池

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